EP3546556B1 - Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel - Google Patents

Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel Download PDF

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Publication number
EP3546556B1
EP3546556B1 EP19165562.0A EP19165562A EP3546556B1 EP 3546556 B1 EP3546556 B1 EP 3546556B1 EP 19165562 A EP19165562 A EP 19165562A EP 3546556 B1 EP3546556 B1 EP 3546556B1
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EP
European Patent Office
Prior art keywords
particle
spray
process according
aqueous mixture
acid
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EP19165562.0A
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English (en)
French (fr)
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EP3546556A1 (de
Inventor
Jose Rodel Mabilangan Caragay
Hossam Hassan Tantawy
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP3546556A1 publication Critical patent/EP3546556A1/de
Priority to US17/034,378 priority Critical patent/US11505768B2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to a process for preparing a spray-dried laundry detergent particle.
  • the particles are substantially free of carbonate salt and have good particle characteristics such as good physical properties, cake strength, flowability as well as good dispensing, dissolution and fabric residue performance (i.e. leave low levels of residue upon laundered fabrics after the laundering process).
  • the particles exhibit a low bulk density.
  • the base particle of a laundry detergent powder is typically prepared by a spray-drying process.
  • detergent ingredients such as detersive surfactant, polymer, filler salt if used, are formed into an aqueous mixture, often called a crutcher mix, and then spray-dried to form a spray-dried laundry detergent particle.
  • This spray-dried particle can be used as a laundry detergent powder product, or (and more usually) the spray-dried particle is mixed with other ingredients such as bleach particles, enzyme particles, perfume, and sometimes additional surfactant particles and other dry-added particles like filler particles such as sodium sulphate particles, to form a fully formulated laundry detergent powder.
  • carbonate salt in the spray-dried base particle, provide not only the alkalinity typically used by the detergent formulator to provide good cleaning ( ⁇ 10.5), but also provides good physical characteristics to the spray-dried base detergent particle. Such physical characteristics include good cake strength and good flowability.
  • silica has been considered as a replacement for the carbonate salt in the spray-dried particle.
  • silica is difficult to handle during the manufacturing process.
  • the very low density and small particle size of silica means complicated and elaborate processing equipment and controls will be needed in order to dose silica in a crutcher mix ahead of spray-drying the mixture to form the spray-dried base particle.
  • the behavior of silica during its introduction into the crutcher mixture is often described as gaseous like, or smoke like, and creates many problems such as dusting, and inaccurate dosing.
  • silica can instead be formed in-situ in the crutcher mixture by the reaction of a water-insoluble silicate salt, which under controlled pH conditions forms silica in an aqueous environment. In order to do this, the pH of the crutcher mixture must be carefully controlled so as to cause this reaction to take place.
  • Water-insoluble silicate salts are conventional detergent ingredient that are often in laundry detergent powders.
  • the manufacturing processes and ways of incorporating water-insoluble silicate salts into the crutcher mixture are well understood.
  • water-insoluble silicate salts can be used as a substrate to form silica in-situ during the spray-drying process.
  • the water-insoluble silicate salts converts to silica, and the resultant spray-dried laundry particles are suitable for use not only in low pH laundry powders, but also in low built laundry powder. Since the water-insoluble silicate salts converts to silica during the manufacturing process, the resultant particle also has the dispensing, dissolution and good fabric residue performance profiles of a low built laundry detergent powder.
  • This process provides a means to produce a spray-dried particle that can be used to formulate a low pH laundry powder, that benefits from the presence of silica, such as good physical characteristics, but without having all of the problems associated with trying to dose silica as a starting ingredient directly into the crutcher mixture.
  • the particles produced by this process also have good dispensing, dissolution and good fabric residue performance profiles.
  • low pH laundry powders tend to have a relatively high bulk density.
  • This tendency to produce spray-dried detergent base particles having higher bulk densities can result in issues when the detergent powder needs to meet certain (low) bulk density requirements which the consumers prefer.
  • this means that (high) bulk density issues can occur in the spray-drying manufacturing plants, and this increase in bulk density needs to be managed so as to negate the increase in bulk density.
  • This in turn can result in the need for complicated air injection systems, which are expensive and bring their own set of issues which need to addressed, or it can result in the need to lower the production rate of the spray-drying manufacturing plant to ensure that the target low bulk density of the resultant spray-dried laundery powder is met.
  • the Inventors have found that the process of the present invention results in the formation of a spray-dried powder that has a lower bulk density.
  • the in-situ formation of silica by the process of the present invention lowers the bulk density of the resultant powder. This overcomes the issues of bulk density discussed above and provides a solution of the bulk density issues and avoids the need for reducing the production rate of a commercial spray-drying laundry detergent plant, or introducing any complicated density management system in a commercial spray-drying laundry detergent plant.
  • the present invention relates to a process for preparing a spray-dried laundry detergent particle, wherein the process comprises the step of contacting water-insoluble silicate salt to monomeric organic carboxylic acid in an aqueous mixture, wherein the aqueous mixture has a pH of 4.2 or less, wherein the aqueous mixture comprises detersive surfactant, and wherein the aqueous mixture is substantially free of carbonate salt, wherein the water-insoluble silicate salt reacts with the monomeric organic carboxylic acid to form silica, wherein the aqueous mixture is spray-dried to form a spray-dried laundry detergent particle, wherein the particle comprises: detersive surfactant; monomeric organic carboxylic acid; and silica, and wherein the particle is substantially free of carbonate salt.
  • the process for preparing a spray-dried laundry detergent particle comprises the step of contacting water-insoluble silicate salt to monomeric organic carboxylic acid in an aqueous mixture, wherein the aqueous mixture has a pH of 4.2 or less, wherein the aqueous mixture comprises detersive surfactant, and wherein the aqueous mixture is substantially free of carbonate salt, wherein the water-insoluble silicate salt reacts with the monomeric organic carboxylic acid to form silica, wherein the aqueous mixture is spray-dried to form a spray-dried laundry detergent particle, wherein the particle comprises: detersive surfactant; monomeric organic carboxylic acid; and silica, and wherein the particle is substantially free of carbonate salt.
  • the steps of forming the aqueous mixture, and spray-drying the aqueous mixture are described in more detail below.
  • the spray-drying process can be carried out using any typical spray-drying equipment.
  • the equipment includes a mixer, typically called a crutcher mixture.
  • second mixers or vessels it is not uncommon for second mixers or vessels to be used after the first mixer, a common example of this is a drop tank.
  • pipes are used, often in combination with one or more pumps to transfer the aqueous mixture from the mixer to a nozzle, where the aqueous mixture is then transferred through the nozzle into a spray-drying tower.
  • a first low pressure pump, followed by a second high pressure pump is used to transfer the aqueous mixture through the pipe.
  • the aqueous mixture is typically formed by contacting detersive surfactant, monomeric organic carboxylic acid, water-insoluble silicate salt and water, It is highly preferred for the detersive surfactant to be present when water-insoluble silicate salt is contacted with monomeric organic carboxylic acid.
  • the preferred order of addition is to contact detersive surfactant with water, then to contact the monomeric carboxylic acid, and then finally contacting the water-insoluble silicate salt.
  • the pH of the aqueous mixture be at 4.2 or less for the production of spray-dried laundry powder having a low bulk density.
  • the pH of the aqueous mixture is 3.5 or less.
  • the water-insoluble silicate salt reacts with the monomeric organic carboxylic acid to form silica. Controlling the weight ratio of monomeric organic carboxylic acid to water-insoluble silicate salt is also a preferred feature of the present invention.
  • the aqueous mixture is substantially free of carbonate salt.
  • substantially free it is typically meant, no deliberately added.
  • silica it can be useful to introduce some alkalinity back into the aqueous mixture, depending on the desired pH of the wash liquor the detergent formulator desires.
  • bulk alkalinity chemistry such as carbonate salt and/or additional silicate salt is not to be used.
  • Alkalinity agents such as NaOH are particularly useful in this regard.
  • the fully formulated laundry detergent powder for which the spray-dried particle can be included is to be such that upon dissolution with water at 20°C and at a concentration of 1g/L in deionsed water, has a pH in the range of from 7.0 to 9.5, preferably from 7.5 to 9.0, or from 7.5 to 8.5.
  • This is considered to be the optimal pH of a low pH laundry detergent powder to provide good fabric care benefits whilst also providing good fabric cleaning performance.
  • the process of the present invention allows the formation of a spray-dried particle having a low pH profile, typically much lower than this optimal pH for the ultimate wash liquor.
  • the spray-dried particle has a pH of 6.0 or less, or even 5.0 or less, or 4.2 or less, or even 3.5 or less upon dissolution in de-ionized water at a concentration of 1g/L and a temperature of 20°C.
  • This pH profile can still be used when formulating a laundry detergent powder, as the spray-dried particle can be combined with other ingredients to raise the pH of the wash liquor back to the ideal pH range described above (e.g. 7.0 to 9.5).
  • the introduction of sodium percarbonate bleach into the laundry powder as a dry-add to be used in combination with the spray-dried base particle is one such alkalinity source.
  • the detergent formulator can take all of this pH effect into account when formulating their desired laundry detergent powder.
  • the spray-drying of the aqueous mixture comprises the steps of transferring the aqueous mixture through a pipe leading through a first pump and then through a second pump to a number of spray nozzles.
  • the first pump is typically a low pressure pump, such as a pump that is capable of generating a pressure of from 3x10 5 to 1x10 6 Pa.
  • the second pump is a high pressure pump, such as a pump that is capable of generating a pressure of from 2x10 6 to 1x10 7 Pa.
  • the pressure in the pipe at the outlet of the first pump may be less than 1x10 6 Pa.
  • the aqueous detergent slurry is transferred through a disintegrator, such as disintegrators supplied by Hosakawa Micron.
  • a disintegrator such as disintegrators supplied by Hosakawa Micron.
  • disintegrators is positioned between the pumps.
  • the flow rate of the aqueous detergent slurry along the pipes is typically in the range of from 800 kg/hour to >50,000 kg/hour.
  • a suitable pressure spray nozzle is a spray systems T4C8 nozzle where multiple nozzles can be used at different levels within the tower.
  • the aqueous detergent slurry is at a temperature of from 60 °C to 130 °C.
  • Suitable spray drying towers are concurrent or counter current spray drying towers, where the latter may be operated as a swirl tower.
  • the inlet air temperature to the spray drying tower is in the range of from 220 °C to 350 °C.
  • the exhaust air temeparture to the spray drying tower is in the range of from 60 °C to 100 °C.
  • the spray-dried powder may be subjected to cooling, for example an air lift.
  • the spray dried powder is subjected to particle size classification to remove oversize material (> 1.8 mm) to form a spray dried powder which is free flowing.
  • Fine material ( ⁇ 0.15 mm) is elutriated with the exhaust air in the spray drying tower and collected in a post tower dust containment system.
  • Aqueous mixture has a pH of 4.2 or less, preferably 3.5 or less.
  • the weight ratio of monomeric organic carboxylic acid to water-insoluble silicate salt present in the aqueous mixture is at least 1.0, preferably at least 1.2, or even at least 1.2, and most preferably at least 1.6. Having an excess of monomeric organic carboxylic acid to water-insoluble silicate salt ensures good reaction kinetics of the formation of silica and also maintains and enables good pH control of the aqueous mixture.
  • the aqueous mixture which can also be known as a crutcher mixture, can also contain other detergent ingredients that are suitable for inclusion into the spray-dried laundry detergent particle. Suitable ingredients are described in more detail below, but include polymers, chelants, hueing dyes, brighteners, colouants and pigments.
  • the aqueous mixture comprises carboxylate polymer.
  • a preferred chemical composition of the aqueous mixture, after the water-insoluble silicate salt has reacted with the monomeric organic carboxylic acid, is such that the aqueous mixture comprises: (a) from 20wt% to 40wt% water; (b) from 7.2wt% to 24wt% detersive surfactant; (c) from 2.4wt% to 8wt% monomeric organic carboxylic acid; (d) from 0.3wt% to 2.4wt% silica; (e) optionally, from 1.2wt% to 8wt% magnesium sulphate; (f) optionally, from 0.3wt% to 4wt% polymer; and (g) optionally, from 21wt% to 64wt% sodium sulphate.
  • Spray-dried laundry detergent particle comprises: detersive surfactant; monomeric organic carboxylic acid; and silica.
  • the particle is substantially free of carbonate salt.
  • the particle may be substantially free of water-insoluble silicate salt.
  • Other ingredients can be included in the particle, these ingredients are described in more detail below.
  • the particle comprises: (a) from 12wt% to 30wt% detersive surfactant; (b) from 4wt% to 10wt% monomeric organic carboxylic acid; (c) from 0.5wt% to 3wt% silica; (d) optionally, from 2wt% to 10wt% magnesium sulphate; (e) optionally, from 0.5wt% to 5wt% polymer; (f) optionally, from 35wt% to 80wt% sodium sulphate ; and (g) optionally, from 0wt% to 6wt% water.
  • the particle may have a pH of 6.0 or less, or 5.0 or less, or 4.2 or less, or 3.5 or less upon dissolution in de-ionized water at a concentration of 10wt% and a temperature of 25°C.
  • the particle may comprise alkalinity agents, a preferred alkalinity agent is NaOH.
  • the particle may comprises magnesium sulphate, preferably the particle comprises magnesium sulphate in amorphous form.
  • the spray-dried particle typically has a bulk density of less than 550g/l.
  • the method of measuring bulk density is described in more detail below.
  • the spray-dried particle typically has a weight average particle size of from 300 micrometers to 600 micrometers.
  • the method of measuring weight average particle size is described in more detail below.
  • the monomeric organic carboxylic acid is preferably a monomeric organic polycarboxylic acid, most preferably citric acid.
  • Suitable acids include: formic acid, acetic acid, propionic acid, butyric acid, caprylic acid and lauric acid, stearic acid, linoleic acid and acrylic acid, methacrylic acid, chloroacetic acid, citric acid, lactic acid, glyoxylic acid, acetoacetic acid, oxalic acid, malonic acid, adipic acid and phenylacetic acid, benzoic acid, salicylic acid, glycine and alanine, valine, aspartic acid, glutamic acid, lysine and phenylalanine, nicotinic acid, picolinic acid, fumaric acid, lactic acid, benzoic acid, glutamic acid; succinic acid, glycolic acid.
  • the organic acid is selected from the group citric acid, malic acid, succinic acid, lactic acid, glycolic acid, fumaric acid, tartaric acid, and formic acids and mixtures thereof. More preferably, the acid is citric acid, lactic acid and tartaric acid. Most preferably is citric acid.
  • Water-insoluble magnesium silicate salt are water-insoluble magnesium silicates salts.
  • a suitable magnesium silicate salt is talc. A method of measuring water-solubility is described in more detail below.
  • Detersive surfactant A preferred detersive surfactant is alkyl benzene sulphonate. Suitable detersive surfactants include anionic detersive surfactants, non-ionic detersive surfactant, cationic detersive surfactants, zwitterionic detersive surfactants and amphoteric detersive surfactants. Suitable detersive surfactants may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
  • Anionic detersive surfactant Suitable anionic detersive surfactants include sulphonate and sulphate detersive surfactants.
  • Suitable sulphonate detersive surfactants include methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably C 10-13 alkyl benzene sulphonate.
  • Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • Suitable sulphate detersive surfactants include alkyl sulphate, preferably C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
  • a preferred sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C 8-18 alkyl alkoxylated sulphate, preferably a C 8-18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C 8-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1.5.
  • alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
  • anionic detersive surfactants include alkyl ether carboxylates.
  • Suitable anionic detersive surfactants may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohols, and any combination thereof. A preferred counterion is sodium.
  • Non-ionic detersive surfactant Suitable non-ionic detersive surfactants are selected from the group consisting of: C 8 -C 18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; alkylpolysaccharides, preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
  • C 8 -C 18 alkyl ethoxylates such as, NEODOL® non-ionic surfactants from Shell
  • Suitable non-ionic detersive surfactants are alkylpolyglucoside and/or an alkyl alkoxylated alcohol.
  • Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, preferably C 8-18 alkyl alkoxylated alcohol, preferably a C 8-18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7.
  • the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
  • Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants.
  • Cationic detersive surfactant Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
  • Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include: halides, preferably chloride; sulphate; and sulphonate.
  • Suitable zwitterionic detersive surfactants include amine oxides and/or betaines.
  • Carboxylate polymer includes polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer.
  • Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of from 4,000 Da to 9,000 Da; maleate/acrylate random copolymers having a molecular weight of from 30,000 Da to 100,000 Da, or from 50,000 Da to 100,000 Da, or from 60,000 Da to 80,000 Da.
  • Another suitable carboxylate polymer is a co-polymer that comprises: (i) from 50 to less than 98 wt% structural units derived from one or more monomers comprising carboxyl groups; (ii) from 1 to less than 49 wt% structural units derived from one or more monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt% structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II): wherein in formula (I), R 0 represents a hydrogen atom or CH 3 group, R represents a CH 2 group, CH 2 CH 2 group or single bond, X represents a number 0-5 provided X represents a number 1-5 when R is a single bond, and R 1 is a hydrogen atom or C 1 to C 20 organic group; wherein in formula (II), R 0 represents a hydrogen atom or CH 3 group, R represents a CH 2 group, CH 2 CH 2 group or single bond,
  • the polymer has a weight average molecular weight of at least 30kDa, or at least 50kDa, or even at least 70kDa.
  • Solid free-flowing particulate laundry detergent composition Typically, the spray-dried particle prepared by the process of the present invention can be combined with other particles to form a solid free-flowing particulate laundry detergent composition that is a fully formulated laundry detergent powder composition.
  • the solid composition comprises a plurality of chemically different particles, such as the spray-dried base detergent particle in combination with one or more agglomerated detergent particles and/or extruded detergent particles.
  • the spray-dried particle may be used in combination with one or more, typically two or more, or five or more, or even ten or more particles selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes; phosphate particles; zeolite particles; polymer particles such as carboxylate polymer particles, cellulosic polymer particles, starch particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol particles; aesthetic particles such as coloured noodles, needles, lamellae particles and ring particles; enzyme particles such as protease granulates, amylase granulates, lipase granulates, cellulase granulates, mannanase granulates, pectate lyase granulates, xyloglucanase granulates, bleaching enzyme granulates and co- granulates of any of these enzymes,
  • the composition may comprise: silicate salt particles, especially sodium silicate particles; and/or carbonate salt particles, especially sodium bicarbonate particles. However it may be preferred for the composition to be free of silicate salt particles, especially free of sodium silicate particles. It may also be preferred for the composition to be free of carbonate salt particles, especially free of sodium carbonate particles.
  • the composition comprises from 1wt% to 10wt% dry-added acid particles, preferably from 2wt% to 8wt% dry-added acid particles.
  • a suitable dry-added acid is an organic acid, preferably a carboxylic acid, preferably cirtric acid.
  • Suitable laundry detergent compositions comprise a detergent ingredient selected from: detersive surfactant, such as anionic detersive surfactants, non-ionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants and amphoteric detersive surfactants; polymers, such as carboxylate polymers, soil release polymer, anti-redeposition polymers, cellulosic polymers and care polymers; bleach, such as sources of hydrogen peroxide, bleach activators, bleach catalysts and pre-formed peracids; photobleach, such as such as zinc and/or aluminium sulphonated phthalocyanine; enzymes, such as proteases, amylases, cellulases, lipases; zeolite builder; phosphate builder; co-builders, such as citric acid and citrate; sulphate salt, such as sodium sulphate; chloride salt, such as sodium chloride; brighteners; chelants; hueing
  • the composition may comprise: silicate salt, especially sodium silicate; and/or carbonate salt, especially sodium bicarbonate and/or sodium carbonate.
  • silicate salt especially sodium silicate
  • carbonate salt especially sodium bicarbonate and/or sodium carbonate.
  • silicate salt especially sodium silicate
  • carbonate salt especially free of sodium carbonate and/or sodium bicarbonate.
  • the composition may have a pH profile such that upon dilution in de-ionized water at a concentration of 1g/L at a temperature of 20oC, the composition has a pH in the range of from 7.0 to 9.5, or from 7.0 to 9.0, or from 7.0 to 8.5, or even from 7.5 to 8.5.
  • Suitable laundry detergent compositions may have a low buffering capacity.
  • Such laundry detergent compositions typically have a reserve alkalinity to pH 7.5 of less than 5.0gNaOH/100g, preferably less than 3.0gNaOH/100g.
  • the composition is preferably substantially free of pre-formed peracid.
  • the composition is prerferably substantially free of phthalimido-peroxycaproic acid. Substantially free means no deliberately added.
  • Detersive Surfactant Suitable detersive surfactants are described above.
  • Suitable polymers include carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, care polymers and any combination thereof.
  • Carboxylate polymer Suitable carboxylate polymers are described above.
  • Soil release polymer The composition may comprise a soil release polymer.
  • a suitable soil release polymer has a structure as defined by one of the following structures (I), (II) or (III): (I) -[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (II) -[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e (III) -[(OCHR 5 -CHR 6 ) c -OR 7 ] f wherein:
  • Anti-redeposition polymer Suitable anti-redeposition polymers include polyethylene glycol polymers and/or polyethyleneimine polymers.
  • Suitable polyethylene glycol polymers include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) hydrophobic side chain(s) selected from the group consisting of: C 4 -C 25 alkyl group, polypropylene, polybutylene, vinyl ester of a saturated C 1 -C 6 mono-carboxylic acid, C 1 -C 6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof.
  • Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains.
  • the average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da.
  • the molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2.
  • the average number of graft sites per 50 ethylene oxide units can be less than 1, or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4.
  • a suitable polyethylene glycol polymer is Sokalan HP22. Suitable polyethylene glycol polymers are described in WO08/007320 .
  • Cellulosic polymer Suitable cellulosic polymers are selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose, sulphoalkyl cellulose, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixures thereof.
  • Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da. Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, e.g. as described in WO09/154933 .
  • Suitable care polymers include cellulosic polymers that are cationically modified or hydrophobically modified. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabric during the laundering cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.
  • Suitable care polymers include dye lock polymers, for example the condensation oligomer produced by the condensation of imidazole and epichlorhydrin, preferably in ratio of 1:4:1.
  • a suitable commercially available dye lock polymer is Polyquart® FDI (Cognis).
  • Suitable care polymers include amino-silicone, which can provide fabric feel benefits and fabric shape retention benefits.
  • Suitable bleach includes sources of hydrogen peroxide, bleach activators, bleach catalysts, pre-formed peracids and any combination thereof.
  • a particularly suitable bleach includes a combination of a source of hydrogen peroxide with a bleach activator and/or a bleach catalyst.
  • Source of hydrogen peroxide include sodium perborate and/or sodium percarbonate.
  • Suitable bleach activators include tetra acetyl ethylene diamine and/or alkyl oxybenzene sulphonate.
  • the composition may comprise a bleach catalyst.
  • Suitable bleach catalysts include oxaziridinium bleach catalysts, transistion metal bleach catalysts, especially manganese and iron bleach catalysts.
  • a suitable bleach catalyst has a structure corresponding to general formula below: wherein R 13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, isodecyl, iso-tridecyl and iso-pentadecyl.
  • Pre-formed peracid include phthalimido-peroxycaproic acid.
  • Enzymes include lipases, proteases, cellulases, amylases and any combination thereof.
  • Suitable proteases include metalloproteases and/or serine proteases.
  • suitable neutral or alkaline proteases include: subtilisins (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and metalloproteases.
  • the suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
  • protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Preferenz P® series of proteases including Preferenz® P280, Preferenz® P281, Preferenz® P2018-C, Preferenz® P2081-WE, Preferenz® P2082-EE and Preferenz® P2083-A/J, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by DuPont, those sold
  • a suitable protease is described in WO11/140316 and WO11/072117 .
  • Amylase Suitable amylases are derived from AA560 alpha amylase endogenous to Bacillus sp. DSM 12649, preferably having the following mutations: R118K, D183*, G184*, N195F, R320K, and/or R458K.
  • Suitable commercially available amylases include Stainzyme®, Stainzyme® Plus, Natalase, Termamyl®, Termamyl® Ultra, Liquezyme® SZ, Duramyl®, Everest® (all Novozymes) and Spezyme® AA, Preferenz S® series of amylases, Purastar® and Purastar® Ox Am, Optisize® HT Plus (all Du Pont).
  • a suitable amylase is described in WO06/002643 .
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
  • cellulases include Celluzyme®, Carezyme®, and Carezyme® Premium, Celluclean® and Whitezyme® (Novozymes A/S), Revitalenz® series of enzymes (Du Pont), and Biotouch® series of enzymes (AB Enzymes).
  • Suitable commercially available cellulases include Carezyme® Premium, Celluclean® Classic. Suitable cellulases are described in WO07/144857 and WO10/056652 .
  • Suitable lipases include those of bacterial, fungal or synthetic origin, and variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces ), e.g., from H. lanuginosa ( T. lanuginosus ).
  • the lipase may be a "first cycle lipase", e.g. such as those described in WO06/090335 and WO13/116261 .
  • the lipase is a first-wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising T231R and/or N233R mutations.
  • Preferred lipases include those sold under the tradenames Lipex®, Lipolex® and Lipoclean® by Novozymes, Bagsvaerd, Denmark.
  • Liprl 139 e.g. as described in WO2013/171241
  • TfuLip2 e.g. as described in WO2011/084412 and WO2013/033318 .
  • Other enzymes are bleaching enzymes, such as peroxidases/oxidases, which include those of plant, bacterial or fungal origin and variants thereof.
  • bleaching enzymes such as peroxidases/oxidases, which include those of plant, bacterial or fungal origin and variants thereof.
  • commercially available peroxidases include Guardzyme® (Novozymes A/S).
  • Other suitable enzymes include choline oxidases and perhydrolases such as those used in Gentle Power BleachTM.
  • Suitable enzymes include pectate lyases sold under the tradenames X-Pect®, Pectaway® (from Novozymes A/S, Bagsvaerd, Denmark) and PrimaGreen® (DuPont) and mannanases sold under the tradenames Mannaway® (Novozymes A/S, Bagsvaerd, Denmark), and Mannastar® (Du Pont).
  • nuclease enzymes such as deoxyribonuclease enzyme.
  • Zeolite builder The composition may comprise zeolite builder.
  • the composition may comprise from 0wt% to 5wt% zeolite builder, or 3wt% zeolite builder.
  • the composition may even be substantially free of zeolite builder; substantially free means "no deliberately added".
  • Typical zeolite builders include zeolite A, zeolite P and zeolite MAP.
  • the composition may comprise phosphate builder.
  • the composition may comprise from 0wt% to 5wt% phosphate builder, or to 3wt%, phosphate builder.
  • the composition may even be substantially free of phosphate builder; substantially free means "no deliberately added".
  • a typical phosphate builder is sodium tri-polyphosphate.
  • Carbonate salt The composition may comprise carbonate salt.
  • the composition may comprise from 0wt% to 5wt% carbonate salt.
  • the composition may even be substantially free of carbonate salt; substantially free means "no deliberately added".
  • Suitable carbonate salts include sodium carbonate and sodium bicarbonate.
  • Silicate salt The composition may comprise silicate salt.
  • the composition may comprise from 0wt% to 5wt% silicate salt.
  • the composition may even be substantially free of silicate salt; substantially free means "no deliberately added".
  • a preferred silicate salt is sodium silicate, especially preferred are sodium silicates having a Na 2 O:SiO 2 ratio of from 1.0 to 2.8, preferably from 1.6 to 2.0.
  • Sulphate salt A suitable sulphate salt is sodium sulphate.
  • Suitable fluorescent brighteners include: di-styryl biphenyl compounds, e.g. Tinopal® CBS-X, di-amino stilbene di-sulfonic acid compounds, e.g. Tinopal® DMS pure Xtra and Blankophor® HRH, and Pyrazoline compounds, e.g. Blankophor® SN, and coumarin compounds, e.g. Tinopal® SWN.
  • Preferred brighteners are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino 1 ,3,5- triazin-2-yl)] amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl.
  • a suitable fluorescent brightener is C.I. Fluorescent Brightener 260, which may be used in its beta or alpha crystalline forms, or a mixture of these forms.
  • the composition may also comprise a chelant selected from: diethylene triamine pentaacetate, diethylene triamine penta(methyl phosphonic acid), ethylene diamine-N'N'-disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid) and hydroxyethane di(methylene phosphonic acid).
  • a preferred chelant is ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP).
  • the composition preferably comprises ethylene diamine-N'N'- disuccinic acid or salt thereof.
  • the ethylene diamine-N'N'-disuccinic acid is in S,S enantiomeric form.
  • the composition comprises 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt.
  • Preferred chelants may also function as calcium carbonate crystal growth inhibitors such as: 1-hydroxyethanediphosphonic acid (HEDP) and salt thereof; N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salt thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid and salt thereof; and combination thereof.
  • HEDP 1-hydroxyethanediphosphonic acid
  • a suitable chelant is MGDA.
  • Hueing agent Suitable hueing agents include small molecule dyes, typically falling into the Colour Index (C.I.) classifications of Acid, Direct, Basic, Reactive (including hydrolysed forms thereof) or Solvent or Disperse dyes, for example classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
  • C.I. Colour Index
  • Solvent or Disperse dyes for example classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
  • Preferred such hueing agents include Acid Violet 50, Direct Violet 9, 66 and 99, Solvent Violet 13 and any combination thereof.
  • hueing agents are known and described in the art which may be suitable for the present invention, such as hueing agents described in WO2014/089386 .
  • Suitable hueing agents include phthalocyanine and azo dye conjugates, such as described in WO2009/069077 .
  • Suitable hueing agents may be alkoxylated. Such alkoxylated compounds may be produced by organic synthesis that may produce a mixture of molecules having different degrees of alkoxylation. Such mixtures may be used directly to provide the hueing agent, or may undergo a purification step to increase the proportion of the target molecule.
  • Suitable hueing agents include alkoxylated bis-azo dyes, such as described in WO2012/054835 , and/or alkoxylated thiophene azo dyes, such as described in WO2008/087497 and WO2012/166768 .
  • the hueing agent may be incorporated into the detergent composition as part of a reaction mixture which is the result of the organic synthesis for a dye molecule, with optional purification step(s).
  • reaction mixtures generally comprise the dye molecule itself and in addition may comprise un-reacted starting materials and/or by-products of the organic synthesis route.
  • Suitable hueing agents can be incorporated into hueing dye particles, such as described in WO 2009/069077 .
  • Suitable dye transfer inhibitors include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone, polyvinylimidazole and mixtures thereof.
  • Preferred are poly(vinyl pyrrolidone), poly(vinylpyridine betaine), poly(vinylpyridine N-oxide), poly(vinyl pyrrolidone-vinyl imidazole) and mixtures thereof.
  • Suitable commercially available dye transfer inhibitors include PVP-K15 and K30 (Ashland), Sokalan® HP165, HP50, HP53, HP59, HP56K, HP56, HP66 (BASF), Chromabond® S-400, S403E and S-100 (Ashland).
  • Suitable perfumes comprise perfume materials selected from the group: (a) perfume materials having a ClogP of less than 3.0 and a boiling point of less than 250°C (quadrant 1 perfume materials); (b) perfume materials having a ClogP of less than 3.0 and a boiling point of 250°C or greater (quadrant 2 perfume materials); (c) perfume materials having a ClogP of 3.0 or greater and a boiling point of less than 250°C (quadrant 3 perfume materials); (d) perfume materials having a ClogP of 3.0 or greater and a boiling point of 250°C or greater (quadrant 4 perfume materials); and (e) mixtures thereof.
  • the perfume may be in the form of a perfume delivery technology. Such delivery technologies further stabilize and enhance the deposition and release of perfume materials from the laundered fabric. Such perfume delivery technologies can also be used to further increase the longevity of perfume release from the laundered fabric. Suitable perfume delivery technologies include: perfume microcapsules, pro-perfumes, polymer assisted deliveries, molecule assisted deliveries, fiber assisted deliveries, amine assisted deliveries, cyclodextrin, starch encapsulated accord, zeolite and other inorganic carriers, and any mixture thereof. A suitable perfume microcapsule is described in WO2009/101593 .
  • Suitable silicones include polydimethylsiloxane and amino-silicones. Suitable silicones are described in WO05075616 .
  • a suitable method of measuring bulk density is adapted from the ISO method number 3424 1975E. Using the specifications described in the ISO method which comprises of a funnel with a lid at the bottom to temporarily hold the powder to be measured and a 500mL cup. Bulk density is measured by placing the powder sample on the funnel while the bottom lid is closed. The cylindrical 500mL cup is weighed and tared on a balance with at least 2 decimal places. The cup is then placed at the bottom of the funnel. Powder is released from the funnel freely by opening the lid, allowing the powder to flow freely and fill the cup. Using a straight edge, carefully level the powder in a serrated motion avoiding additional vibration. Once the powder has been levelled, the cup which had been previously tared on the balance is then weighed. The weight of the powder in 500ml container is multiplied by 2 to get the bulk density as grams per Liter
  • Weight average particle can be measured using a dynamic image analyzer (e.g. CamSizer by Retzsch). Powder samples are taken online by an automatic sampler. Approximately 15g of blown powder is sampled and measured using a vibratory aluminium feeder with speed start level set at 40% and a nominal area of 3%. The particles drop between a planar light source with two CCD cameras. The particles projected shadows are analysed and median particle size (D50) is calculated using the software provided by the manufacturer based on the calculated volume assuming a spherically shaped particle. The analysis takes approximately 1200 images within 1 minute.
  • a dynamic image analyzer e.g. CamSizer by Retzsch. Powder samples are taken online by an automatic sampler. Approximately 15g of blown powder is sampled and measured using a vibratory aluminium feeder with speed start level set at 40% and a nominal area of 3%. The particles drop between a planar light source with two CCD cameras. The particles projected shadows are analysed and median particle size (D50) is calculated using the software provided by the
  • a suitable method uses 2 grams (on a solid basis, excluding water content) of a sample (such as a silicate salt) in a 100g total solution using a deionised water.
  • the sample is kept at 20°C by using a water bath as needed.
  • the mixture is placed in a 500mL beaker with a diameter 80mm and a stirrer bar length of 50 mm set at 500rpm.
  • the mixture is mixed for 30 minutes to allow dissolution and/or dispersion of the samples. Once the mixture has been thoroughly mixed, it is then passed through a stainless steel filter with an aperture size of 25 micrometers (25 microns).
  • the filtration uses a 3-piece glass Buchner funnel (9 cm diameter), 1 L flask and a vacuum pump with water trap and a 9 cm diameter stainless steel filter.
  • a pre-weighed stainless steel dry filter is placed on the Buchner funnel. While the vacuum pump is on, the mixture that has been previously mixed is then poured onto the filter. Once all the liquid has thoroughly drain out of the filter, the vacuum pump is stopped.
  • the stainless steel filter with the wet residue is then dried inside at 100°C oven for 24 hours. The filter is then reweighed. The difference between this and the initial weight prior to the filtration is taken as the weight of insoluble retained on the filter. % insoluble is calculated.
  • any silicate salt having less 0.50% or more insoluble in the above described method is considered to be a water-insoluble silicate salt.
  • Example 1B Insoluble Silicate Example -High pH
  • Detergent slurries were prepared using a hot water jacketed, top entry mixer with anchor blades and a separate high shear flat blade disperser. The batch size was fixed at 55kg and the end of the batch temperature was set at 85°C. Materials were added sequentially one by one as shown on the table for each example. Anchor blade rpm was set to 50 rpm from the beginning and was changed to 90 rpm prior to the addition of Na2SO 4 . High shear disperser was turned on at 1000rpm while sodium sulphate powder was being added to the crutcher. Once all the ingredients have been added, the recycle line was turned on, keeping the high shear disperser on for the next 5 minutes. Batch cycle time was around 30 minutes.
  • the high shear disperser and the recirculation was turned off.
  • the flow was then diverted to the atomizing nozzle.
  • the slurry at around 3 to 4 bar was pumped through an IKA rotor stator high speed mixer. Once it passed the high-speed mixer, it went to the externally atomized 2-fluid nozzle with an internal diameter of 2 mm. Slurry rates were kept constant at an average of 40 kg/hr for all the batches.
  • a fluidised spray dryer was used to dry the slurries to blown granules.
  • the dryer consists of a spray dryer chamber and a 2-stage fluid bed dryer at the bottom of the spray drying chamber.
  • the inlet air which entered at the top of the main chamber had a temperature of 300°C which was kept constant throughout. Exhaust air exited from the top of the main chamber along with the fines. Fines were separated via cyclone from the exhaust air and recycled back to the top of the main chamber.
  • the outer fluid bed temperature was kept in the range of 85 to 105°C while the inner bed temperature was varied to achieve a blown powder moisture between 1 to 2%.
  • the powder that came out of the fluid bed was conveyed to the sampling points for pH, particle size and bulk density analysis.
  • the pH of the aqueous mixture measured at 10% solution at 20°C when the source of silica (talc) was contacted to the citric acid (addition sequence 5) was 2.784.
  • Citric Acid a) 3.6467 Monosodium Citrate (a) 2.9667 Disodium Citrate (a) 0.0533 Hydrophobically modified acrylic base polymer 2.6000 C1 2 -14 Alkyl Benzene Sulphonate Paste 19.5000 MgSO4 4.0500 Na2SO4 62.3278 SiO2 from Talc 0.9850 Added Water 2.0000 Miscellaneous 1.8706 Total 100.0000

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Claims (15)

  1. Verfahren zur Herstellung eines sprühgetrockneten Wäschewaschm ittelteilchens,
    wobei das Verfahren den Schritt des Inkontaktbringens von wasserunlöslichem Magnesiumsilikatsalz mit monomerer organischer Carbonsäure in einer wässrigen Mischung umfasst,
    wobei die wässrige Mischung einen pH-Wert von 4,2 oder weniger aufweist,
    wobei die wässrige Mischung Reinigungstensid umfasst, wobei die wässrige Mischung im Wesentlichen frei von Carbonatsalz ist,
    wobei das wasserunlösliche Magnesiumsilikatsalz mit der monomeren organischen Carbonsäure zur Bildung von Silica umgesetzt wird,
    wobei die wässrige Mischung sprühgetrocknet wird, um ein sprühgetrocknetes Wäschewaschmittelteilchen zu bilden, wobei das Teilchen umfasst: Reinigungstensid; monomere organische Carbonsäure; und Silica,
    wobei das Teilchen im Wesentlichen frei von Carbonatsalz ist.
  2. Verfahren nach Anspruch 1, wobei die wässrige Mischung einen pH-Wert von 3,5 oder weniger aufweist.
  3. Verfahren nach einem der vorstehenden Ansprüche, wobei das Teilchen bei Auflösung in entionisiertem Wasser bei einer Konzentration von 10 Gew.-% und einer Temperatur von 25 °C einen pH-Wert von 6,0 oder weniger aufweist.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei das Teilchen bei Auflösung in entionisiertem Wasser bei einer Konzentration von 10 Gew.-% und einer Temperatur von 25 °C einen pH-Wert von 4,2 oder weniger aufweist.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei das Teilchen bei Auflösung in entionisiertem Wasser bei einer Konzentration von 10 Gew.-% und einer Temperatur von 20 °C einen pH-Wert von 3,5 oder weniger aufweist.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei es sich bei der monomeren organischen Carbonsäure um eine monomere organische Polycarbonsäure handelt.
  7. Verfahren nach Anspruch 6, wobei es sich bei der monomeren organischen Polycarbonsäure um Citronensäure handelt.
  8. Verfahren nach einem der vorstehenden Ansprüche, wobei das Reinigungstensid Alkylbenzolsulfonat ist.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei das Gewichtsverhältnis von monomerer organischer Carbonsäure zu wasserunlöslichem Magnesiumsilikatsalz, das in der wässrigen Mischung vorliegt, mindestens 1,6 beträgt.
  10. Verfahren nach einem der vorstehenden Ansprüche, wobei die wässrige Mischung Magnesiumsulfat umfasst, und wobei das Teilchen Magnesiumsulfat in amorpher Form umfasst.
  11. Verfahren nach einem der vorstehenden Ansprüche, wobei die wässrige Mischung Carboxylatpolymer umfasst und wobei das Teilchen Carboxylatpolymer umfasst.
  12. Verfahren nach einem der vorstehenden Ansprüche, wobei das Teilchen umfasst:
    (a) zu von 12 Gew.-% bis 30 Gew.-% Reinigungstensid;
    (b) zu von 4 Gew.-% bis 10 Gew.-% monomere organische Carbonsäure;
    (c) zu von 0,5 Gew.-% bis 3 Gew.-% Silica;
    (d) wahlweise zu von 2 Gew.-% bis 10 Gew.-% Magnesiumsulfat;
    (e) wahlweise zu von 0,5 Gew.-% bis 5 Gew.-% Polymer;
    (f) wahlweise zu von 35 Gew.-% bis 80 Gew.-% Natriumsulfat; und
    (g) wahlweise zu von 0 Gew.-% bis 6 Gew.-% Wasser.
  13. Verfahren nach einem der vorstehenden Ansprüche, wobei, nachdem das wasserunlösliche Magnesiumsilikatsalz mit der monomeren organischen Carbonsäure umgesetzt wurde, die wässrige Mischung umfasst:
    (a) zu von 20 Gew.-% bis 40 Gew.-% Wasser;
    (b) zu von 7,2 Gew.-% bis 24 Gew.-% Reinigungstensid;
    (c) zu von 2,4 Gew.-% bis 8 Gew.-% monomere organische Carbonsäure;
    (d) zu von 0,3 Gew.-% bis 2,4 Gew.-% Silica;
    (e) wahlweise zu von 1,2 Gew.-% bis 8 Gew.-% Magnesiumsulfat;
    (f) wahlweise zu von 0,3 Gew.-% bis 4 Gew.-% Polymer; und
    (g) wahlweise zu von 21 Gew.-% bis 64 Gew.-% Natriumsulfat.
  14. Verfahren nach einem der vorstehenden Ansprüche, wobei das sprühgetrocknete Wäschewaschmittelteilchen eine Schüttdichte von weniger als 550 g/l aufweist.
  15. Verfahren nach einem der vorstehenden Ansprüche, wobei das sprühgetrocknete Wäschewaschmittelteilchen eine gewichtsgemittelte Teilchengröße von 300 Mikrometern bis 600 Mikrometern aufweist.
EP19165562.0A 2018-03-28 2019-03-27 Verfahren zur herstellung von sprühgetrocknetem waschmittelpartikel Active EP3546556B1 (de)

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JP2021516273A (ja) 2021-07-01
CN111742040A (zh) 2020-10-02
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